Fuel oil composition



Patented July 20,1954

FUEL OIL COMPOSITIDN John B. R. Caron, North Plainfield, N. J Calmy Wies, New York, N. Y., and Everett B. Glendenning, Cranford, N. J., assignors to Shell Development Company, Emeryville, Calif., a corporation of Delaware No Drawing. Application March 13, 1951, Serial No. 215,384

8 Claims.

This invention pertains to improvement of hydrocarbon fuels, and more particularly to fuel oil compositions capable of preventing or inhibiting the sludging and/or clogging tendencies generally exhibited by hydrocarbon fuels, such as those utilized in burner systems, tanks, diesel and combustion engines, and other industrial and domestic equipment. In addition, this invention relates to fuel oil compositions capable of removing preformed deleterious matter from filters, screens, and the like which deleterious matter is formed by deterioration and/or the presence of foreign bodies, (e. g., water) in the fuel oils.

Hydrocarbons, such as distillate fuels, for example, those having a normal distillation range of from about 300 F. to about 700 F., and particularly those from about 340 F. to about 640 F., generally have a marked tendency to deteriorate under oxidizing conditions, and to form sludge, Also, the presence of impurities in such fuels, such as the presence of moisture, dispersed water, organic and/or inorganic foreign matter, and the like, causes the formation of insoluble products which tend to settle out and adhere to surfaces with which they come in contact, thereby in turn, causing clogging of plugging of filters, strainers, screens, conduit lines, and the like, of the equipment in which they are used. This necessitates frequent cleaning and even replacement of parts, thereby markedly decreasing the performance efiiciency of various equipment which utilizes such fuel oils.

The problem of screen clogging is common, particularly in domestic fuel oil systems employing distillate fuel oils produced by distilling or cracking of petroleum, which fuels are characterized by their relatively low viscosity and other properties. Fuel oils of this type generally conform to the specifications set forth in Commercial Standards 0. S. l2-40 for Nos. 1, 2, and 3, Fuel Oils. Petroleum distillates within the ranges specified and which generally do not exceed 700 F., and preferably are below 675 F., for use as diesel fuels, are further examples of the type of oils which under conditions described herein have a tendency to clog screens or filters, particularly when such fuels contain minor amounts of water dispersed therein.

Another place where screen clogging and plugging of conduit lines is encountered is in fuel oil storage tanks, which latter may be connected to burner systems or engines, etc. The stored fuel generally comes in contact with air, moisture, etc., which cause formation and precipitation of sludge materials, the latter depositing on and clogging the screens or filters used for protecting the burners or engines using such fuel oils.

It is an object of this invention to inhibit sludging tendencies of hydrocarbon fuel oils. It is another object to inhibit sludging and precipitation of contaminants in hydrocarbon distillate fuel oils, particularly in cracked hydrocarbon fuels. It is still another object to provide distillate fuel oils, particularly fuel oils obtained during cracking of hydrocarbons, which fuel oils have excellent performance characteristics with respect to freedom from screen clogging, even after extensive storage under oxidizing conditions and in the presence of water. Still another object is to provide a distillate fuel oil composition which is effective in removing preformed sludge deposits formed in fuel oil systems. Still another object is to provide a particular type of distillate fuel oil composition or a blend thereof, which is noncorrosive, stable, and effective for removing sludge and for cleaning metal surfaces.

The above and other objects of this invention may be attained by dispersing, admixing with or dissolving in hydrocarbon fuel oils (which normally have a tendency to cause clogging or plu ging of screens or the like), a minor amount, which amount, however, is suflicient to inihibit said tendencie of one or more surface-active, non-ash forming oil-soluble amines, amides thereof, and the like, said nitrogen-containing compounds having one or more than one hydrocarbyl radical having at least 14 carbon atoms; said hydrocarbyl radical can contain polar substituents such as halo, cyano, sulfo, keto, carboxyl, hydroxyl, thiol, etc.

The hydrocarbon distillate fuel oils in which the active ingredient and/or ingredients of this invention are dispersed or dissolved may be treated or untreated cracked fuel oils, or mixtures of cracked fuels with straight run fuel oils, said fuel oils having components normally distilling from about 300 F. to about 700" F. Preferred fuels have a boiling range of from about 340 F. to about F., and particularly from about 400 F. to about 675 F. Specifically, hydrocarbon distillates which are utilized as bases in compositions of this invention are cracked gas oils, fuel oils, furnace oils, burner oils, diesel fuel oils, kerosene, etc., or mixtures of said cracked fuels with the corresponding or like straight run hydrocarbon fractions.

Fuel oils which have marked tendencies towards sludging and clogging of screens, filters, etc., are primarily cracked or blends of cracked and straight run fuel oils which have the following properties:

Gravity, API 29-35 ASTM dist. F.:

LBP 406-500 EBP 600-700 Sulfur percent W 0.5-1.05 Carbon residue (10 Btms) percent W 0.1-0.4 Pour point, F -15 The oil soluble amines or derivatives thereof which possess the above-outlined properties include: mono, di and tri tetradecyl, hezadecyl, octadecyl, octadecadienyl, oleyl, ricinoleyl, abietyl amines; wax amines prepared by chlorination of parafiin wax and ammonolysis of the product: cyclo-aliphatic amines, e. g. tetradecyl cyclohexylamine, octadecyl cyclohexylamine, octadecyl dicyclohexylamine; heterocyclic amines, e. g., octadecenyl morpholine, octadecenyl piperidine, octadecenyl pyridine, etc.; polyamines, e. N-nhexadecyl diethylene triamine, N-octadeoenyl ethylene diamine and the like.

Preferred nitrogen compounds are: octadecylamine, dioctadecylamine, trioctadecylamine, oleylamine, dioleylamine, trioleylamine, dihexadecylamine, dihexadecyloctadecylamine, hexadecyloctadecylamine, tetradecylcyclohexylamine, octadecylmorpholine; octadecylamin-e oil-soluble petroleum sulfonate, trioctadecylamine oil-soluble petroleum sulfonate, octadecyl mo-rpholine oil-soluble petroleum sulfonate.

If desired, and under certain conditions of use, it is preferred to add detergents to compositions of this invention. The function of the detergent agents in compositions of this invention is to act as peptizers and aid in inhibiting or preventing the settling and adhering of impurities and sludge to surfaces and allow any impurities present or formed to pass through the screen or filter system.

Detergents which may be used are alkali, alkaline earth and heavy metals and organic nitrogen base salts of various organic acids. The acidic portion of such detergents may be naphthenic acid, sulfonic acids, aromatic and hydroxy aromatic carboxylic acids, aliphatic acids, said acids containing, if desired, substituent groups, e. g., an amino, hydroxide, mercapto, halo and sulfur groups and the like. Also phenates, alcoholates, carbamates, thiocarbamates, xanthates,

etc., may be used.

Particularly preferred class of detergents are the salts of alkyl substituted phenol sulfides or its selenide and/or telluride equivalent. These phenolic salts may be represented by the general formulas:

wherein M is a metal; R and R represent at least one alkyl radical attached to the aromatic ring Ar, the total number of carbon atoms in all of such radicals being at least 5; X is O and/or S; Q is S, Se, or Te or a methylene group, and n is an integer of from 1 to 4.

To form the salts of these phenolic compounds they may be treated with such metal compounds as Li, Na, K, Cu, Hg, Fe, Mn, Mg, Ca, Ba, Sr, Pb,

Ni, Co, Cr, Sn, Fe, etc. Alkaline earth metals are particularly preferred because of their solubility in hydrocarbons and potent detergent properties.

In addition to the normal salts of phenolic compounds, basic salts may be used and can be represented by the formula wherein the symbols are the same as referred to in the previous formulas. These basic salts may be formed by reacting the aromatic acidic compounds with more than the amount of metal 0X- ide or hydroxide necessary to form the normal salt.

Some specific compounds as represented by the above formulas are: barium tertiary octyl phenol sulfide and disulfide, barium ditertiary amyl phenol sulfide, calcium iso-hexadecyl phenol sulfide, magnesium tertiary amyl phenol sulfide, cobalt tertiary amyl phenol sulfide, barium dodecyl salicylate sulfide, sulfide of the barium salt of the ethyl ester of p-hydroXy dithiobenzoic acid, calcium octyl phenol selenide, Ca salt of octylphenol-formaldehyde condensation product, etc. The amount of detergent salt used may vary from between about 5 and 15% and preferable is kept below 10 Another preferred class of detergents comprises the alkali (e.. g. Na, K, Li) and/ or alkaline earth metal (e. g. Ca, Sr, Ba, Mg) salts of petroleum sulfonic acids, preferably of high molecular weight, derived from petroleum hydrocarbon crudes and fractions thereof which are of the socalled mixed type, i. e. containing naphthenic type hydrocarbons.

These oil-soluble petroleum sulfonates may be obtained by various processes, such as those disclosed in the U. S. Patents 2,388,677, 2,395,713, 2,413,713, 2,413,311, 2,414,773, 2,416,397, and if desired, purified by such means as those disclosed in U. S. Patents 2,236,933, 2,334,532, 2,357,- 366, 2,368,452, and 2,406,753.

The metal salts of the specific type of petroleum sulfonic acid under discussion, or the other types of detergents, may be added to the concentrate or base in amounts of from about 5% to about 15%, and preferably in amounts below 10%.

In systems wherein substantial amounts of moisture are present, a drying agent may be added which is compatible with the active ingredients of this invention. By tying up most of the free moisture in this manner, the amount which would normally combine with sludgeforming materials is diminished, thus alleviating a most aggravating clogging problem.

Drying agents which are particularly suited are the glycol-ether type such as diethylene glycol mono-methyl, ethyl N- and isopropyl ether, diethylene glycol mono-butyl ether, diethylene glycol mono-decyl ether, etc., also dipropylene glycol mono-ethyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol mono-isoamyl ether, diisobutylene glycol mono-isopropyl ether, ethylene-propylene glycol mono-ethyl ether, ethylene isobutylene glycol mono isopropyl ether, etc. Instead of the glycol-ether, various alcohols may be used such as diols having 6 or more carbon atoms in the molecule such as hexylene glycol, decylene glycol, cetylene glycols, etc. diglycols such as dipropylene glycols, dibuc mlwn 4,. M

tylene glycol, diamylene glycol, ether alcohols and particularly the glycol mono-alkyl ethers, e. g., the Cellosolves such as ethylene glycol mono-ethyl ether, ethylene glycol mono-propyl 6. detergent to about 0.002%, drying agent 0 to about 0.26%.

The following illustrates the effectiveness of compositions of this invention as sludge inhibiether, ethylene glycol mono-tert-butyl ether, tors and anti-clogging agents. ethylene glycol mono-butyl ether, propylene gly- Example I col mono-ethyl ether, propylene glycol mono-isoamyl ether, etc Also glycol mono tert, butyl To a number of sample bottles each containether, ethylene glycol mono-hexyl-butyl ether, ing DP Y 50 00- Of u Oil n y propylene glycol mono-isoamyl ether, etc. Also susceptible to c use clo a minute amount glycerine and the like may be used, of about 0.15 cc. of water was added and also to The following is a general formula of a base each Sample tt about 0.05% f a sp fi base composition f this invention; composition as noted in the table below was also added. The bottles were shaken thoroughly and Surface actw? agent g-hlgh molecular then permitted to stand for about one hour. Welght ammes as defined above Suspension properties of water and inert par- Detergent e. g. phenate, metal sulfonate, ticles were observed and noted after one hour. 9- 040% After one hour of standing the bottles were Drymg agent glycol-ether 050% shaken again and the contents poured into a very Hydrocarbon fuel O11 Balance fine strainer container. Wetting and drainage Specific base (concentrate) compositions may p p rties on the bott e were rv j t be illustrated by t following m fore and after removal of contents. The time of efllux of the composition was noted for each composltw" A composition and the condition of the strainer Per cent observed. Octadecylamine 4 Ethylene glycol monobutyl ether 10 Example H Hydrocarbon fuel 1 3 Another test, the results of which are also tabulated below, in order to determine the ef- Composztwn C fectiveness of compositions of this invention for Per cent anti-sludging and clogging properties, was con- Dodecyl methylene tljlamme 10 ducted in the following manner. About 0.05% Hydrocarbon fuel on 90 of base compositions of this invention was added Composition E to fuel oils containing entrained moisture. The Per cent 3 samples were allowed to age for two days. These Dodecyl diethylene triamine 15 samples were then shaken and evaluated for Barium salt of alkyl phenol disulfide 10 their anti-clogging properties, as related in the Hydrocarbon fuel oil '75 preceding paragraph.

Properties evaluated immediately Same properties after aging of doped @0576 or less base after adding concentrate to fuel oil fuel oil gig gg fi ggf g g Example I Example II trained moisture Strainer Drainage Suspension Strainer Drainage Suspension CompcsitionA Excellent. Excellent. Excellent Excellent Excellent- Excellent. Undoped Fuel Oil Poor Poor Poor Poor Poor Poor.

Composition G Per cent Octadecylamine l5 Barium salt of alkyl phenol disulfide 5 Sodium petroleum sulfonate 5 Hydrocarbon fuel oil '75 Composition H Per cent Dodecyl diethylene triamine l5 Barium salt of alkyl phenol disulfide 5 Sodium petroleum sulfonate 5 Hydrocarbon fuel oil 75 To compositions of this invention may be added minor amounts of a foaming inhibitor such as silicon liquids, e. g. dimethyl silicone, fiuoro organic compounds, chloro paraffins, salts of alkyl alkylene phosphates and the like. Compositions of this invention may be used to remove deposits, formed on metal surfaces such as in tubes, evaporators, heat exchangers, distillation and cracking equipment and the like. They are non-corrosive and do not interfere wtih the functioning of the liquid in which dispersed.

It is to be understood that while the features of the invention have been described and illustrated in connection with certain specific examples of this invention, however, is not to be limited thereto or otherwise restricted, except by the prior art and the scope of the appended claims.

This application is a continuation-in-part of application Serial No. 37,085, filed July 3, 1948, which has matured into U. S. Patent 2,553,183.

We claim as our invention:

1. A finished non-ash distillate fuel oil containing a substantial amount of cracked components and entrained moisture to which nonclogging properties have been imparted by the incorporation therein from about 0.002% to about 0.05% by weight of octadecylamine.

2. A finished non-ash distillate fuel oil con taining a substantial amount of cracked components and entrained moisture to which nonclogging properties have been imparted by the incorporation of about 1 pint of a concentrate consisting of a hydrocarbon oil containing from about 4% to about 20% by weight of an oilsoluble aliphatic amine having at least one alkyl chain of at least 14 carbon atoms and up to 18 carbon atoms, to 200 to 1000 gallons of fuel oil.

3. A non-ash containing anti-clogging concentrate adapted to be added to a hydrocarbon fuel oil, said concentrate consisting essentially of a major amount of a liquid hydrocarbon distillate fraction containing a substantial amount of cracked components and from about 4% to about 20% by Weight of an oil-soluble aliphatic amine having at least one alkyl radical of at least 14 carbon atoms and up to 18 carbon atoms.

4. A non-ash containing anti-clogging concentrate adapted to be added to a hydrocarbon fuel oil, said concentrate consisting essentially of a major amount of a liquid hydrocarbon distillate fraction containing a substantial amount of cracked components and from about 4% to about 20% by weight of octadecylamine.

5. A concentrate according to claim 4 containing in addition thereto up to 10% of a metal salt of alkyl phenol disulfide.

6. A concentrate according to claim 4 containing in addition thereto up to 10% of a metal oil-soluble petroleum sulfonate.

7. A concentrate according to claim 4 containing in addition thereto up to 10% of a sodium oil-soluble petroleum sulfonate.

8. A concentrate according to claim 4 containing in addition thereto up to 50% of a glycol ether as a drying agent.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,246,842 De Groote June 24, 1941 2,385,158 Paulsen Sept. 18, 1945 2,409,687 Rogers et al Oct. 22, 1946 2,433,243 Smith et a1 Dec. 23, 1947 2,433,716 Smith et a1. Dec. 30, 1947 2,487,189 Smith et a1 Nov. 8, 1949 2,487,190 Smith et a1. Nov. 8, 1949 2,527,987 Caron et a1 Oct. 31, 1950 

2. A FINISHED NON-ASH DISTILATE FUEL OIL CONTAINING A SUBSTANTIAL AMOUNT OF CRACKED COMPONENTS AND ENTRAINED MOISTURE TO WHICH NONCLOGGING PROPERTIES HAVE BEEN IMPARTED BY THE INCORPORATION OF ABOUT 1 PINT OF A CONCENTRATE CONSISTING OF A HYDROCARBON OIL CONTAINING FROM ABOUT 4% TO ABOUT 20% BY WEIGHT OF AN OILSOLUBLE ALIPHATIC AMINE HAVING AT LEAST ONE ALKYL CHAIN OF AT LEAST 14 CARBON ATOMS AND UP TO 18 CARBON ATOMS, TO 200 TO 1000 GALLONS OF FUEL OIL. 